Wetland Use in Acid Mine Drainage Remediation

Steven White

ABSTRACT
There are estimates that 557,000 abandoned mines exist in the U.S. (Costello 2003),
mostly coal mines in the western portion of the country. Many of these mines have no
wastewater control features and become flooded over time. The ensuing highly acidic
(pH~3) wastewater is laden with toxic heavy metals (Gibert et al. 2004). One method
used to treat acid mine drainage is to divert water through wetlands. In wetlands,
increasing pH and alkalinity influences heavy metal concentrations, while microbial and
plant activity mineralizes contaminants to form precipitates. Different approaches can be
taken to neutralize and remove targeted heavy metals, from aerobic wetlands for iron,
anaerobic wetlands for other sulfides and metals, and using lime to influence pH and
alkalinity.

KEYWORDS
Acid Mine Drainage (AMD), Remediation, Wetlands, Mine-Water Chemistry

INTRODUCTION: ACID MINE DRAINAGE

Abandoned and active mines are a major pollution concern. In 1989, it was estimated
that ca. 19,300 km of streams and rivers, and ca. 72,000 ha of lakes and reservoirs
worldwide had been seriously damaged by mine effluents (Johnson and Hallberg
2005a). The U.S. Forest Service estimates that there are between 20,000 and 50,000
mines actively producing acid drainage in the western U.S. that affects between 8,000
and 16,000km of streams (Schlesinger 2002), while estimates from the Mineral Policy
Center project that there are 557,000 abandoned mines in the U.S. (Costello 2003). The
waters draining from these mines are often acidic and contain elevated concentrations of
heavy metals (iron, aluminum, and magnesium) and metalloids (arsenic).

Active mines are only a minor concern compared to abandoned mines. Active mines
may be deep and well below the water table, but pumping water out of the mine or
lowering the water table keeps the water pollution to minimal levels. Once mines are
abandoned and pumping ceases, the water table rises. Contaminated groundwater is then
able to discharge from the mine, compounding the pollution problems. Some case
studies included in this paper are the Wheal Jane mine, which in 1992 had 50,000m3 of
acid mine drainage (AMD) released into the environment (Hallberg and Johnson 2005a),
as well as mines in Korea and India.

In deep mining, large tunnels and slopes were cut down to coal deposits (Earth
Conservancy, 2000). These mines usually have remnants of coal veins that were left to

26-1
support the mine structure. Mine openings and outfalls are two primary sources of AMD
leaving mines. Outfalls are points of overflow from deep mines and are caused by holes
that were drilled into the mine structure to relieve water accumulation when the mine was
active. Another source of AMD is derived from culm banks that consist of separated
rock and coal removed from the mine. Culm banks are generally stored outdoors
exposed to precipitation, which develops into AMD.

Mine Water Chemistry

The chemical composition of AMD can be complex, often depending on the geological
formations found in the mine. Treating AMD is pivotal on what pollutants compositions
are found in the waste stream. The following section details a few of the main heavy
metals found in AMD.

Pyrite
The oxidation of iron pyrite (FeS2) is one of the major sources of pollution. Pyrite is the
worlds most abundant sulfide mineral, and is present with most sulfide ores. The
concentrations of pyrite in coal deposits are generally between 1-20 % (Johnson and
Hallberg 2005a). Equation 1 shows a condensed formula for the reaction that occurs,
which actually takes place over 4 steps.

4 FeS2 + 15 O2 + 14 H20 4 Fe(OH)3 + 8 SO42- + 16 H+ (1)

Acidity
Acidic mine waters are typically caused by the oxidative dissolution of sulfide minerals,
such as pyrite. The generation of free protons from the hydrolysis of metals, (Equation 2-
5) causes a mineral acidity to develop (Hallberg and Johnson 2005a, Costello 2003). The
acidic nature of mine wastes is also dependant on chemical concentrations in the area.
Due to that, AMD covers a wide scope of toxic concentrations and pH levels.

Al3+ + 3 H2O Al(OH)3 + 3H+ (2)

Fe+3 + 3H2O Fe(OH)3 + 3H+ (3)
Fe+2 + 0.25 O2(aq) + 2.5 H2O Fe(OH)3 + 2H+ (4)
Mn+2 + 0.25 O2(aq) + 2.5 H2O Mn(OH)3 + 2H+ (5)

There are also a variety of other reactions that contribute to the creation AMD, such as
Equations 6-11 (Costello 2003).

Sphalerite: ZnS(s) + 2O2(aq) Zn+2 + SO4 -2 (6)

Galena: PbS(s) + 2O2(aq) Pb+2 + SO4 -2 (7)
Millerite: NiS(s) + 2O2(aq) Ni+2 + SO4 -2 (8)
Greenockite: CdS(s) + 2O2(aq) Cd+2 + SO4 -2 (9)
Covellite: CuS(s) + 2O2(aq) Cu+2 + SO4 -2 (10)
Chalcopyrite: CuFeS2(s) + 4O2(aq) Cu+2 + Fe+2 + SO4 -2 (11)

26-2
 WASEWATER TREATMENT BY WETLANDS
Due to the large area of some abandoned mines, inhibiting the formation and release of
waste drainage is impractical. That observation means that wastewater must be treated
after it leaves the mine (Hallberg and Johnson 2005a). There are several active and
passive methods being explored to treat AMD (see figure 1). The more cost intensive
active systems include adding lime, aeration, off-line sulfidogenic bioreactors. Active
treatment methods generally accrue more financial costs due to constant operation and
maintenance fees (chemicals, mechanical systems) (Costello 2003). Passive systems
include using anoxic limestone drains, aerobic wetlands, compost reactors, permeable
reactive barriers, and packed bed iron-oxidation bioreactors. Wetlands have become a
favorable option in comparison to other treatment methods because of the wetland is
relatively self-sustaining once established, and wetlands are cheaper than active treatment
systems.

Figure 1: Available Acid Mine Drainage Remediation Options (Johnson, et al. 2003).

26-3
The first attempts of using wetlands for AMD were in 1984, when Wieder and Lang
detected that AMD that flowed through a bog was cleaner (Kalin 2004, Johnson et al.
2002). Further trials using bogs proved to less successful, but they did present evidence
that microbial activity plays an active part in mineralizing metals into stable compounds
and adding alkalinity to wastewater.

Figure 2. Schematic cross-sectional diagrams of four different pond treatment

components. http://www.facstaff.bucknell.edu/kirby/4ponds.html

Aerobic Wetlands
Aerobic wetlands are primarily used when iron is the main contaminant. Aerobic
wetlands also require net alkaline waters that are able to buffer an increase in hydrogen
ions released from metal hydrolysis reactions. Aerobic wetlands generally are shallow
and include plant to immobilize heavy metals (see figure 2). The main drawback to
aerobic wetlands is that over time the accumulation of precipitate will severely limit their

26-4
remediation abilities. Periodic removal of precipitates is necessary, either through
flushing the area or dredging (Costello 2003).

Anaerobic Compost Reactors with Wetlands

When waters are net acidic, the pH must be raised and ideally the waters will be
bought to net alkaline conditions. When iron and aluminum are the main
contaminants then alkaline addition followed by an aerobic settling pond is often
used to precipitate metals and raise pH. The most common wetland application
for hard rock mines aims to establish sulfate-reducing bacteria under anaerobic
conditions and, as a result of the bacterias metabolic needs, metals are
precipitated as sulfides, (Costello 2003).

Anaerobic wetlands generally are accompanied by some form of bioreactor or chemical

addition in order to control the pH and alkalinity.

Bioreactors
Passive bioreactors are defined as lined trenches and pits containing a mixture of
organic matter and/or alkaline agent. Some examples of bioreactor fillings include
compost, cobbles, animal waste, food processing waste, and crushed lime. The purpose
of bioreactors is to adjust the pH of the AMD and to establish desired microorganisms
(Costello 2003, Hallberg and Johnson 2005b).

Chemical Additions
Another approach used to increase the alkalinity in AMD wetland systems is the addition
of lime into the system (see figure 2 for two examples of lime addition). The addition of
lime (calcium carbonate) raises the pH of the wastewater by reacting with hydronion ions
(Equations 12 & 13). Lime also adds alkalinity to the water by producing bicarbonate
ions (Costello 2003, Younger et al., 2002). One option is to use an anoxic limestone
drain that adds alkali to the AMD but does not oxidize ferrous iron to form precipitates
(Johnson and Hallberg 2005a). It is important to limit iron precipitates on the limestone
because the iron will dramatically decrease the effectiveness of the limestone.
+ +2
CaCO3 + 2H Ca + H2O + CO2 (12)
CaCO3 + H2CO3 Ca+2 + 2HCO3- (13)

Other chemicals that can be used to increase alkalinity include hydrated lime (calcium
hydroxide), soda ash (sodium carbonate), caustic soda (sodium hydroxide), and
ammonia (Costello 2003).

26-5
 Microbial Activities

Figure 3: Possible pathways in the cycling of carbon in the mine waste environment (Ledin et al. 1996).

Microorganisms fulfill important roles in the creation and remediation of AMD. In

regards to microorganisms causing AMD, the activities of acidophilic
microorganisms in abandoned mines causes an increase in oxidation reactions.
Many of the microbial processes that can change metal mobility occur in
drainage water from mine waste, (Costello 2003). In the case of bioremediation
of AMD, microorganisms can also cause metal to become immobilized and
generate alkali (see figure 3 for possible metabolic pathways).

26-6
Acidophilic microorganisms generally favor the environmental conditions seen in
AMD, and the iron-oxidizing bacteria such as Acidithiobacillus ferrooxidans and
Leptospirillum ferrooxidans tend to flourish in mine waters (Hallberg and Johnson
2005a). . Once acidophilic bacteria are established, there is the possibility that
they will increase chemical reactions involved in acid mine drainage,
compounding the problem (Costello, 2003).Iron-oxidizing bacteria can precipitate
ferric iron out of the AMD to improve water conditions.

In terms of the operation of the treatment system, it is important to note that the
presence of these versatile microbes in the water will compromise such a
treatment system should any ferrous iron be present in these effluents as well.
The iron-oxidizing Thiomonas will catalyze the oxidation of the ferrous iron to
ferric iron. The subsequent hydrolysis of the ferric iron will generate more
acidity, essentially leading to a reversal of the whole AMD remediation process
(Hallberg and Johnson 2005a).

Bacteria, such as species of Thiomonas, are able to oxidize reduced sulfur compounds as
well as oxidize ferrous iron in aerobic conditions (Hallberg and Johnson 2005a).
Plant Activities

Plant Activity Phytoremediation

Phytoremediation is defined the use of green plants and their associated microbiota,
soil amendments, and agronomic techniques to remove, contain, or render harmless
environmental contaminants, (Costello 2003). There are several factors that must be
addressed when studying the effectiveness of plants in AMD treatment. Ideal plants must
be hardy; able to tolerate low nutrient levels, be resistant to weather shifts, and uptake
more contaminants than normal plants. Determining acceptable plants for use in AMD
remediation becomes difficult because of the specific characteristics displayed by plant
species. There are 300 documented species that are capable of hyperaccumulating nickel,
26 cobalt, 24 copper, 19 selenium, 16 zinc, 11 manganese, 1 thallium, and 1 cadmium
(Brooks et al. 1998, Costello 2003).

The use of phytoremediation is generally accompanied by other forms of treatment, such

as bioreactors. Plant activity must be monitored to assure the system is effective and to
determine the spread of immobilized contaminants. The initial uptake of heavy metals is
sometimes associated with soil parameters more than plant types (Bogan and Sullivan
2003). As the soil becomes saturated, heavy metal seepage will minimize the effects of
phytoremediation. Another negative aspect of using plants for AMD treatment is that
caution must be taken to avoid animal consumption of contaminated vegetation (Costello
2003, Sheoran and Sheoran 2005, Collins et al. 2004).

26-7
Conclusion
Wetlands have proven to be effective in treating AMD in ideal conditions. While the
source of pollution remains un-dealt with, the spread of pollution remains contained to
the soil and plant life in the treatment system.

.we are still not addressing the origins of the problem, that is, reaction rates and the
contaminant generating process. Treatment approaches must be assessed for their
effectiveness on appropriate time scales if we are to find truly sustainable solutions.
There is no doubt that passive treatment systems and/or constructed wetlands effectively
reduce organic water pollution. But when the run-off from mining wastes flow through
wetlands, the deposition of metals onto adsorption sites can overload them, leading to
system failure and wetland destruction (Kalin 2004).

Fluctuations in source water (flooding, droughts) and the eventual buildup of precipitates
lead to lower AMD remediation and are negative aspects of using wetlands. Wetlands
also are ineffective in areas with rocky soils and steep slopes. Close proximity to floods
and large land requirements negatively impact wetland use. Yet the cost of using active
treatment methods as opposed to passive treatments is not practical due to the nature of
the problem. The majority of mines producing AMD in the U.S. currently have
inefficient treatment systems, making active treatment financial improbable.

26-8
REFERENCES

Banks, D.; Younger, P.; Amesen, R.; Iversen, E.; Banks, S. (1997) Mine-Water
Chemistry: the Good, the Bad and the Ugly. Environmental Geology, 32, 157.

Bogan, B.; Sullivan, W. (2003) Physicochemical Soil Parameters Affecting Sequestration

and Mycobacterial Biodegradation of Polycyclic Aromatic Hydrocarbons in Soil.
Chemosphere, 52, 1717.

Collins, B.; McArthur, V.; Sharitz, R. (2004) Plant Effects on Microbial Assemblages
and Remediation of Acidic Coal Pile Runoff in Mesocosm Treatment Wetlands.
Ecological Engineering, 23, 107.

Costello, C. (2003) Acid Mine Drainage: Innovative Treatment Technologies. U.S.

Environmental Protection Agency, Office of Solid Waste and Emergency
Response Technology Innovation Office, Washington, D.C.

Earth Conservancy (2000) Acid Mine Drainage: A Solution to Pollution. Green Works,
http://www.greenworks.tv/waterquality/acidmindrainage.htm, Date Accessed:
11/20/05.

Gibert, O.; Pablo, J.; Cortina, J.; Ayora, C. (2004) Chemical Characterization of Natural
Organic Substrates for Biological Mitigation of Acid Mine Drainage. Water
Research, 38, 4186.

Hallberg, K.; Johnson, B. (2005) Biological Manganese Removal from Acid Mine
Drainage in Constructed Wetlands and Prototype Bioreactors. Science of the
Total Environment, 338, 115.

Hallberg, K.; Johnson, B. (2005) Microbiology of a Wetland Ecosystem Constructed to

Remediate Mine Drainage from a Heavy Metal Mine. Science of the Total
Environment, 338, 53.

Johnson, B.; Hallberg, K. (2005) Acid Mine Drainage Remediation Options: A Review.
Science of the Total Environment, 338, 3.

Johnson, D.; Hallberg, K. (2003) Pitfalls of Passive Mine Water Treatment.

Environmental Science & Bio/Technology, 1, 335.

Johnson, D. (1995) Acidophilic Microbial Communities: Candidates for Bioremediation

of Acidic Mine Effluents. Proceedings of the 1995 International Biodeterioration
& Biodegradation, 41.

Johnson, D. (2002) Chemical and Microbiological Characteristics of Mineral Spoils and

Drainage Waters at Abandoned Coal and Metal Mines. Water, Air, and Soil
Pollution, 3, 47.

26-9
Kalin, M (2004) Passive Mine Water Treatment: The Correct Approach? Ecological
Engineering, 22, 299.

Lee, J.; Chon, H. (2005) Hydrogeochemical Characteristics of Acid Mine Drainage in

Vicinity of an Abandoned Mine, Daduk Creek, Korea. Journal or Geochemical
Exploration, Article in Press.

Ledin, M.; Pedersen, K. (1996) The Environmental Impact of Mine Wastes Roles of
Microorganisms and Their Significance in Treatment of Mine Wastes. Earth-
Science Reviews, 41, 67.

Mays, P.; Edwards, G. (2001) Comparison of Heavy Metal Accumulation in a Natural

Wetland and Constructed Wetlands Receiving Acid Mine Drainage. Ecological
Engineering, 16, 487.

Natarajan, K.; Subramanian, S.; Braun, J. (2005) Environmental Impact of Metal Mining
Biotechnological Aspects of Water Pollution and Remediation An Indian
Experience. Journal of Geochemical Exploration, Article in Press.

Schlesinger, M. (2002) Fact Sheet Acid Mine Drainage. Northern Alaska

Environmental Center,
http://www.northern.org/artman/publish/acidminedrainage.pdf, Date Accessed:
11/20/05.

Sheoran, A.; Sheoran, V. (2005) Heavy Metal Removal Mechanism of Acid Mine
Drainage in Wetlands: A Critical Review. Minerals Engineering, Article in Press.

Tanner, C.; Nguyen, M.; Sukias, J (2005) Nutrient Removal by a Constructed Wetland
Treating Subsurface Drainage from Grazed Dairy Pasture. Agriculture,
Ecosystems and Environment, 105, 145.

Tarutis, W.; Stark, L.; Williams, F. (1999) Sizing and Performance Estimation of Coal
Mine Drainage Wetlands. Ecological Engineering, 12, 353.

Whitehead, P.; Cosby, B.; Prior, H. (2005) The Wheal Jane Wetlands Model for
Bioremediation of Acid Mine Drainage. Science of the Total Environment, 338,
125.

Whitehead, P.; Hall, G.; Neal, C.; Prior, H. (2005) Chemical Behavior of the Wheal Jane
Bioremediation System. Science of the Total Environment, 338, 41.

Woulds, C.; Ngwenya, B. (2004) Geochemical Processes Governing the Performance of

a Constructed Wetland Treating Acid Mine Drainage, Central Scotland. Applied
Geochemistry, 19, 1773.

26-10